We report on the observation of two distinct photogenerated negative trion states T A and T B in two-dimensional tungsten disulfide (2D-WS 2) monolayers. These trions are postulated to emerge from their parent excitons X A and X B, which originate from spin-orbit-split (SOS) levels in the conduction band (CB) and valence band (VB). Time-resolved spectroscopy measurements suggests that Pauli blocking controls a competition process between T A and T B photoformation, following dissociation of X A and X B through hole trapping at internal or substrate defect sites. While T A arises directly from its parent X A, T B emerges through a different transition accessible only after X B dissociates through a hole trapping channel. This discovery of additional optically-active band-edge transitions in atomically-thin metal dichalcogenides may revolutionize optoelectronic applications and fundamental research opportunities for many-body interaction physics. Ultrafast pump-probe spectroscopy of two-dimensional tungsten disulfide monolayers (2D-WS 2) grown on sapphire substrates revealed two transient absorption spectral peaks that are attributed to distinct negative trions at ~2.02 eV (T 1) and ~1.98 eV (T 2). The dynamics measurements indicate that trion formation by the probe is enabled by photodoped electrons that remain after trapping of holes from excitonsmore » or free electron-hole pairs at defect sites in the crystal or on the substrate. Dynamics of the excitons X A and X B’s characteristic absorption bands, at ~2.03 and ~2.40 eV, respectively, were separately monitored and compared with the photoinduced absorption features. Selective excitation of the lowest exciton level X A using λ pump < 2.4 eV forms only trion T 1, which implies that the electron that remains from the dissociation of exciton X A is involved in the creation of this trion with a binding energy ~ 10 meV with respect to X A. The absorption peak that corresponds to trion T 2 appears when λ pump > 2.4 eV, which is just sufficient to excite exciton X B. The dynamics of trion T 2 formation are found to correlate with the disappearance of the bleach of X B exciton, which indicates the involvement of holes participating in the bleach dynamics of exciton X B. Static electrical-doping photoabsorption measurements confirm the presence of an induced absorption peak similar to that of T 2. Since the proposed trion formation process here involves exciton dissociation through hole-trapping by defects in the 2D crystal or substrate, this discovery highlights the strong role that defects have in defining the optical and electrical properties of 2D metal chalcogenides, which is relevant to a broad spectrum of basic science and technology applications.« less

@article{osti_1222550,
title = {Observation of two distinct negative trions in tungsten disulfide monolayers},
author = {Boulesbaa, Abdelaziz and Huang, Bing and Wang, Kai and Lin, Ming-Wei and Mahjouri-Samani, Masoud and Rouleau, Christopher M. and Xiao, Kai and Yoon, Mina and Sumpter, Bobby G. and Puretzky, Alexander A. and Geohegan, David B.},
abstractNote = {We report on the observation of two distinct photogenerated negative trion states TA and TB in two-dimensional tungsten disulfide (2D-WS2) monolayers. These trions are postulated to emerge from their parent excitons XA and XB, which originate from spin-orbit-split (SOS) levels in the conduction band (CB) and valence band (VB). Time-resolved spectroscopy measurements suggests that Pauli blocking controls a competition process between TA and TB photoformation, following dissociation of XA and XB through hole trapping at internal or substrate defect sites. While TA arises directly from its parent XA, TB emerges through a different transition accessible only after XB dissociates through a hole trapping channel. This discovery of additional optically-active band-edge transitions in atomically-thin metal dichalcogenides may revolutionize optoelectronic applications and fundamental research opportunities for many-body interaction physics. Ultrafast pump-probe spectroscopy of two-dimensional tungsten disulfide monolayers (2D-WS2) grown on sapphire substrates revealed two transient absorption spectral peaks that are attributed to distinct negative trions at ~2.02 eV (T1) and ~1.98 eV (T2). The dynamics measurements indicate that trion formation by the probe is enabled by photodoped electrons that remain after trapping of holes from excitons or free electron-hole pairs at defect sites in the crystal or on the substrate. Dynamics of the excitons XA and XB’s characteristic absorption bands, at ~2.03 and ~2.40 eV, respectively, were separately monitored and compared with the photoinduced absorption features. Selective excitation of the lowest exciton level XA using λpump < 2.4 eV forms only trion T1, which implies that the electron that remains from the dissociation of exciton XA is involved in the creation of this trion with a binding energy ~ 10 meV with respect to XA. The absorption peak that corresponds to trion T2 appears when λpump > 2.4 eV, which is just sufficient to excite exciton XB. The dynamics of trion T2 formation are found to correlate with the disappearance of the bleach of XB exciton, which indicates the involvement of holes participating in the bleach dynamics of exciton XB. Static electrical-doping photoabsorption measurements confirm the presence of an induced absorption peak similar to that of T2. Since the proposed trion formation process here involves exciton dissociation through hole-trapping by defects in the 2D crystal or substrate, this discovery highlights the strong role that defects have in defining the optical and electrical properties of 2D metal chalcogenides, which is relevant to a broad spectrum of basic science and technology applications.},
doi = {10.1103/PhysRevB.92.115443},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 11-15,
volume = 92,
place = {United States},
year = {2015},
month = {9}
}

We report that transition metal dichalcogenides (TMDs) such as WS 2 show exciting promise in electronic and optoelectronic applications. Significant variations in the transport, Raman, and photoluminescence (PL) can be found in the literature, yet it is rarely addressed why this is. In this report, Raman and PL of monolayered WS 2 produced via different methods are studied and distinct features that indicate the degree of crystallinity of the material are observed. While the intensity of the LA(M) Raman mode is found to be a useful indicator to assess the crystallinity, PL is drastically more sensitive to the quality ofmore » the material than Raman spectroscopy. We also show that even exfoliated crystals, which are usually regarded as the most pristine material, can contain large amounts of defects that would not be apparent without Raman and PL measurements. Ultimately, these findings can be applied to the understanding of other two-dimensional heterostructured systems.« less

Pressure-induced structural and electronic transformations of tungsten disulfide (WS 2) have been studied to 60 GPa, in both hydrostatic and non-hydrostatic conditions, using four-probe electrical resistance measurements, micro-Raman spectroscopy and synchrotron x-ray diffraction. Our results show the evidence for an isostructural phase transition from hexagonal 2H c phase to hexagonal 2H a phase, which accompanies the metallization at ~37 GPa. This isostructural transition occurs displacively over a large pressure range between 15 and 45 GPa and is driven by the presence of strong shear stress developed in the layer structure of WS 2 under non-hydrostatic compression. Interestingly, this transition ismore » absent in hydrostatic conditions using He pressure medium, underscoring its strong dependence on the state of stress. We also attribute the absence to the incorporation of He atoms between the layers, mitigating the development of shear stress. We also conjecture a possibility of magnetic ordering in WS 2 that may occur at low temperature near the metallization.« less

Two-dimensional tungsten disulfide (WS 2) is an emerging semiconducting photocatalyst featuring high optical absorption, carrier mobility, and catalytic activity toward hydrogen evolution. While characterization of its optical and electrocatalytic properties has advanced, less is known about its ultrafast carrier dynamics and intrinsic photocatalytic activity in aqueous systems producing hydrogen. This work removed extraneous variables often found in photoelectrochemical systems, thereby allowing the intrinsic proton reduction rate for monolayer-rich WS2 nanosheets to be estimated via transient absorption lifetimes and a developed kinetic scheme. Addition of a hole scavenger, ascorbic acid (AA), resulted in a 3-fold increase in carrier lifetimes following photoexcitation.more » Longer electron lifetimes with AA yielded a 14-fold increase in hydrogen production. An intrinsic proton reduction rate constant was extracted that may be extended to any photoelectrochemical or electrochemical hydrogen evolution scheme involving small, monolayer-rich WS 2 catalysts. This represents an important step in better understanding catalytic systems utilizing TMD catalysts.« less